JOURNAL OF MEMBRANE SCIENCE
·
2025
·
IF 9
Bin Liu,Xinyue Cui,Xiaozhen Lu,Xuewu Zhu,Lin Wang,Junyong Zhu
Positively charged polyamide (PA) nanofiltration (NF) membranes with sub-nanopores show promise for lithium extraction from salt-lake brines with high Mg 2+ /Li + ratios. This study introduces the use of triamino guanidine (TG), a highly positively charged molecule, to regulate grafting on monolayer PA membranes, resulting in dual-layer (PEI-TMC-TG) NF membranes. The monolayer PA membranes were created via spin-coating assisted interfacial polymerization between polyethyleneimine (PEI) and tricarbonyl chloride (TMC). The PEI/TMC-TG NF membranes exhibited several advantages over unmodified PEI-TMC NF membranes, including higher positive charge density, narrower pore size distribution, excellent hydrophilicity, and a more porous separation layer microstructure. Experimental results indicated that enhanced Donnan effect, size sieving, and dielectric repulsion within the sub-nanopores contributed to exceptional Li + /Mg 2+ selectivity during filtration of East Taijiner brine (S Li + /Mg 2+ = 64.5). Furthermore, the TG hydrophilic layer significantly improved water permeability (15.4 LMH/bar) and long-term stability. To reduce membrane fouling in the charge-positive NF process by removing organic matter from complex salt lake brine, we explored electrocoagulation as a pre-treatment method and identified optimal conditions for the EC-NF process. This strategy maximizes sustainable lithium recovery from brine in an economically viable green manner while enhancing the efficiency of NF membranes for lithium extraction from salt lakes.
研究领域:
环境科学
·
材料科学
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2022
·
IF 10.53
Shiyu Zhang,Runnan Zhang,Runlai Li,Zixuan Zhang,Yafei Li,Hao Deng,Junhui Zhao,Tianrun Gu,Mengying Long,Xiaoyao Wang,Sui Zhang,Zhongyi Jiang
Positively charged nanofiltration membranes hold great potential in Li + /Mg 2+ separation, but their application in alkaline solutions, such as alkaline salt-lake brines has not been reported. Herein, inspired by the arginine's unique structure and biological function, we explore superstrong basic triaminoguanidine (TG) molecule as aqueous monomer to fabricate positively charged polyamide nanofiltration membranes for Li + /Mg 2+ separation. With the Li + /Mg 2+ mass ratios of 1:50 and 1:120, at pH 9.6, the separation factors (S Li,Mg ) of membranes reach 31.8 and 20.9. Meanwhile, at pH 5.6, the S Li,Mg are 46.4 and 36.4, which are the ever-reported highest value and such high S Li,Mg can be well retained in the pH range of 5.6–8.6. The superior Li + /Mg 2+ selectivity stems from the superhigh protonation capacity of guanidine groups in a broad pH range.
研究领域:
材料科学
·
化学工程
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Quan Li,Yahui Liu,Yunling Jia,Yanhong Ji,Feng Yan,Jianxin Li,Younas Mohammad,Benqiao He
Constructing a suitable charged surface layer of nanofiltration (NF) membrane is one of the key challenges to achieve efficient Li + /Mg 2+ separation performance with high Mg 2+ /Li + mass ratio ( W Mg2+/Li+ ). Herein, we proposed a facile route, i.e., grafting the short chain amino-rich monomers (SCA, H(NHCH 2 CH 2 ) 1-4 -NH 2 ) instead of conventional amino-rich macro-monomers (ARM), to construct a separation layer with uniform positive charge on the surface of pristine polyamide (PA) NF membrane to achieve effective Li + /Mg 2+ separation. The SCA grafted NF membrane (PA-g-SCA) retained a more uniform distribution of positively charged groups on the PA layer compared with ARM grafted NF membrane. The SCA grafted NF membrane exhibited a high rejection of Mg 2+ and high permeation of Li + at the same time, leading to an extremely high separation factor for Li + /Mg 2+ of 130 even in the W Mg2+/Li+ of 200:1 in the feed, which greatly surpassed those reported. The pure water flux was 1.8 folds than that of the pristine NF membrane due to the hydrophilicity improvement. The results suggested that the distribution uniformity of positive charges could be the key to efficient Li + /Mg 2+ separation of the NF membrane. Our study provided a facile and robust route to design and construct high Li + /Mg 2+ separation performance NF membranes.
研究领域:
材料科学
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环境工程
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高影响因子
ACS Nano
·
2026
·Vol. 20
·期 37
·25629-25641
·
IF 17.3
Deng Hao,Zhu Yong,Xu Kai,Pang Xiao,Lu Yanqiu,Zheng Yu,Wang Ying,Lyu Bohui,Zhang Runnan,Jiang Zhongyi,Zhang Sui
Covalent organic framework (COF) nanosheets are ideal
building
blocks for fabricating high-performance membranes. The production
of COF nanosheets in water is a significant step towards sustainable
synthesis but remains an unresolved challenge. Herein, we report an
aqueous synthesis method for COF nanosheets via a group capping-decapping
strategy. The in-plane-dominated COF growth is driven by two factors:
first, capping of aldehyde groups with secondary amines enhances monomer
solubility in water for homogeneous nucleation; second, the presence
of ionic groups on amine monomers suppresses out-of-plane stacking
via electrostatic repulsion. By adjusting Brønsted acids or bases
concentrations, the decapping rate and the subsequent COF polymerization
rate can be tuned, enabling precise control over the reaction kinetics.
Consequently, highly crystalline ionic COF nanosheets can be mildly
synthesized in water with high volumetric yield and at a gram scale.
The COF composite membranes assembled from nanosheets and polyethylenimine
exhibit high selectivity and outstanding Li + recovery efficiency
for Li + /Mg 2+ separation. Furthermore, the excellent
processability of COF nanosheets is demonstrated by fabricating the
tubular membrane module.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2026
·
IF 12.5
Zhicheng Wang,Xin Shi,Zizhen Peng,Wenzhong Ma,Yakai Lin,Hideto Matsuyama,Qiuyan Bi
A SISAIP strategy was developed to regulate interfacial PA formation. • SDS/NaCl regulation produced ultrathin PA layers with sub-nanometer pathways. • The membrane achieved S Li, Mg of 90.9 and permeance of 9.5 L m −2 h −1 bar −1 . • Stable operation and strong flux recovery were obtained under brine-relevant tests. The rapidly increasing global demand for lithium has stimulated the development of advanced membrane technologies for lithium extraction from salt-lake brines. Nanofiltration (NF) membranes with precisely regulated subnanometer transport pathways are highly attractive for Li + /Mg 2+ separation; however, the rational construction of selective layers that simultaneously deliver high ion selectivity and fast water transport remains challenging. Herein, we report a scalable surfactant–inorganic salt–assisted interfacial polymerization (IP) strategy, termed SISAIP, to fabricate high-performance polyamide NF membranes. Interfacial tension, dynamic light scattering, and UV–vis analyses indicated that sodium dodecyl sulfate enriched at the water/oil interface and regulated PEI transport across the interface, whereas NaCl modified the aqueous-phase microenvironment, moderated PEI diffusion toward the interface, and helped confine the interfacial reaction zone. This coordinated regulation produced an ultrathin PA selective layer with an apparent thickness of 11.2 ± 0.6 nm and compact subnanometer transport pathways. The optimized membrane achieved a water permeance of 9.5 L·m −2 ·h −1 ·bar −1 , an S Li,Mg of 90.9, and Mg 2+ rejection above 99.5%, corresponding to 578.6% and 437.9% increases in water permeance and S Li,Mg over the control T-IP membrane, respectively. The membrane also maintained stable performance during 120 h of continuous filtration and exhibited favorable fouling/scaling resistance, with a flux recovery ratio of 100% under organic-conditioned CaSO 4 scaling conditions. This SISAIP strategy provides a promising and scalable route for designing advanced NF membranes toward efficient lithium recovery from salt-lake brines.
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2025
·
IF 9
Ting Qi,Xiaona Wei,Xianfu Chen,Tiandan Lu,Dongliang Jin,Jing Zhong
Nanofiltration (NF) membranes are emerging as promising candidates for lithium extraction. However, their performance is challenged by the comparable physicochemical characteristics of Li + and Mg 2+ . In this work, a dual-reinforcement strategy is proposed to simultaneously enhance both selectivity and permeability by combining the densification of the polyamide (PA) network and the construction of Li + -selective transport channels. During the interfacial polymerization of piperazine (PIP) and trimesoyl chloride (TMC), the cross-linking density of the PA layer is increased by adding sodium dodecyl sulfate (SDS), while Li + -selective transport nanochannels are constructed by incorporating 15-crown-5 ether (CE). This synergistic modification enhances Mg 2+ rejection via intensified size exclusion and facilitates Li + permeation through ion-specific recognition. The resulting PIP/SDS/CE-PA membrane exhibits a high cross-linking degree of 91.26 %, a reduced pore size of 0.70 nm, and a narrow pore size distribution (σ = 1.22). Molecular dynamics simulations confirm the preferential complexation of CE with Li + , and that Li + exhibits faster and more favourable translocation in the PIP/SDS/CE-PA membranes, thereby facilitating its selective transport. Experimentally, the membrane achieves a high MgCl 2 rejection of 97.1 % and a low LiCl rejection of 56.7 %, yielding an exceptional Li + /Mg 2+ selectivity of 30 in a MgCl 2 /LiCl binary system, while maintaining a water permeance of 5 L m −2 h −1 bar −1 . These findings demonstrate the strong potential of the PIP/SDS/CE-PA membrane for the direct treatment of high Mg 2+ /Li + ratio salt-lake brines and offer a versatile strategy for designing next-generation NF membranes for selective ion separations.
研究领域:
材料科学
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膜技术
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分离科学
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环境工程
·
能源材料
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高影响因子
DESALINATION
·
2025
·
IF 9.8
Yang Zhao,Tao Wu,Yanliang Wang,Zimo Feng,Lijuan Cheng,Yu Zheng,Hui Wang,Kai Xu,Runnan Zhang,Zhongyi Jiang
Increasing the positive charge density (PCD) of nanofiltration (NF) membranes is crucial to acquiring the high selectivity of Li + /Mg 2+ separation and remains extensive exploitation. Herein, a novel modifier (1-methyl hydrazide-3,5-dibenzyl trimethyl ammonium bromide, MDTAB) containing two quaternary ammonium groups and an amino group was designed and synthesized, which was grafted onto the polyamide NF membrane surface. The surface PCD of the MDTAB modified membrane (+7.02 mC m −2 ) was almost four times that of the unmodified membrane, which is the highest among the existing positively charged NF membranes. The MDTAB modified membrane acquired MgCl 2 rejection as high as 99.3 %, and the pure water permeance was 15.92 L·m −2 ·h −1 ·bar −1 . When utilized for Li + /Mg 2+ separation, the Mg 2+ /Li + mass ratio was reduced from the original 100 to 1.73. This strategy may provide valuable guidance for the rational design of the positively charged membrane in salt lake lithium extraction applications.
研究领域:
材料科学
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化学工程
·
环境科学
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高影响因子
Journal of Physical Chemistry C
·
2023
·
IF 3.7
Shuai Wang,Liuyuan Zhu,Rujie Yang,Minliang Li,Fangfang Dai,Shiqi Sheng,Liang Chen,Shanshan Liang
Lithium extraction from brine or seawater using membrane technology has attracted extensive attention in recent years. Graphene oxide (GO), as one of the two-dimensional materials, has been proven as a competitive candidate for membranes. However, the GO membranes still suffer challenges for ion sieving due to the swelling in the aqueous solution. In this work, a GO–PEI membrane with positively charged channels was constructed by polyelectrolyte polyethyleneimine (PEI) molecular chain-grafted GO nanosheets. The GO–PEI membrane showed a high selectivity of 22.2 for Li+/Mg2+, together with a competitive Li+ permeation rate of 0.09 mol m–2 h–1 in a binary permeation test. In addition, the membrane showed excellent stability during the separation process. The enhanced Li+/Mg2+ separation performance of the GO–PEI membrane could be mainly attributed to the synergistic effect of size sieving and electrostatic repulsion. We further systematically studied the influence of various variables, such as PEI molecular weight, PEI content, membrane thickness, and ion concentration, on separation performance. This work deepens the understanding of membrane ion selectivity from multiple perspectives and puts forward a strategy to design a two-dimensional membrane structure from microscopic materials.
研究领域:
材料科学
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环境科学
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Wenguang Wang,Chao Wang,Yanqiu Zhang,Hanyang Xu,Lu Shao
Advanced monovalent cation exchange membranes (MCEMs) have been applied to extract key monovalent cations (Li + or Na + ) from nature, but it is challenging to design high-performance MCEMs with low membrane area resistance and specific charge properties. Herein, a positively-charged Fe 3+ -bridged pyrogallic/polyethyleneimine membrane (Fe 3+ -bridged PY/PEIM) for efficient Li + /Mg 2+ separation is fabricated through a covalent bond and coordination bond (CB/COB) competitive reaction. Various physicochemical characterizations elucidate that the formation of COBs reduces the reaction sites of PY and PEI molecules for Michael-addition and Schiff-base reactions, which reduces the thickness of the selective layers to reduce the membrane area resistance from 6.58 to 4.83 Ω·cm 2 . A highly positively-charged selective layer caused by unreacted NH 2 groups and Fe 3+ makes the optimal Fe 3+ -bridged PY/PEIM exhibit a superior separation performance (perm-selectivity (Li + /Mg 2+ ) of 45.57 with a Li + flux of 4.61 × 10 −8 mol·cm −2 ·s −1 ). Moreover, the optimal Fe 3+ -bridged PY/PEIM also has excellent separation performance (high Li + flux and perm-selectivity) and operational stability when treating three simulated solutions with different Mg/Li mass ratios and salinities. The new strategy for constructing a thin, defect-free and positively-charged selective layer through a CB/COB competitive reaction can provide new insights for designing high-performance MCEMs towards environmental remediation and energy harvesting.
研究领域:
材料科学
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环境科学
·
能源技术
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DOI
高影响因子
AICHE JOURNAL
·
2025
·
IF 4
Wenyu Shen,Yang Li,Shaoyang Gao,Yuhe Tian,Ziyun Zhang,Junbo Xu,Duo Wang,Chao Yang
Synergetic extraction system has been extensively applied in Li extraction to alleviate the increasingly severe shortage of lithium production. However, the underlying coordination mechanisms still remain unclear. Herein, a synergistic extraction system of sodium tetraphenylborate (NaBPh 4 ) and tributyl phosphate (TBP) was employed for Li + /Mg 2+ separation. With increasing TBP content in the organic phase, Li + extraction efficiency gradually rose from 88.64% to 92.20%. By contrast, Mg 2+ extraction efficiency presented an abnormal trend, which was an initial decrease followed by a gradual increase. High-resolution electrospray ionization mass spectrometry together with quantum chemical calculations revealed that Mg 2+ mainly formed Mg(BPh 4 ) 2 at the low TBP content whereas the formed complex gradually transitioned to [Mg · 4TBP](BPh 4 ) 2 with increasing TBP content, leading to the initial decline in Mg 2+ extraction efficiency. Our work provides valuable insights into the mechanisms underlying Li + /Mg 2+ separation in the TBP system and offers a promising approach for broader applications.
研究领域:
湿法冶金
·
分离科学
·
无机化学
·
资源回收
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DOI
高影响因子
DESALINATION
·
2026
·
IF 9.9
Haoran Zhang,Qingbai Chen,Jinye Zhang,Di Wang,Ping Li,Haoxue Wang,Min Zhang,Yong Xu,Jianyou Wang,Zhenliang Xu
Innovatively developed an “adhesion-assisted growth” strategy for fabricating MOF membranes. • Constructed dual-confined ion channels enabling highly selective lithium-ion transport. • Implemented seed implantation in the adhesive layer to induce rapid and well-ordered MOF growth. • Established interconnected interface architecture forming continuous ion transport networks. • The developed membrane exhibits excellent long-term operational stability. Membranes featuring ordered biomimetic ion channels have been widely explored for ion-sieving applications, such as lithium extraction from salt-lake brines, seawater desalination, and energy conversion. However, achieving high ion permselectivity while enabling scalable fabrication for industrial use remains a major challenge. Here, we report a dual-confined metal-organic framework (MOF) membrane fabricated via an “adhesion-assisted growth” strategy. By integrating biomimetic ion channels functionalized with acidic groups, precise pore-size control, and surface chemical modulation, the membrane establishes a dual-nanoconfined separation system that simultaneously enables efficient Li + transport and effective Mg 2+ rejection. This specially designed adhesive layer not only promotes the well-defined formation of the MOF layer but also creates an interconnected ion transport network, thereby accelerating ion migration during selective electrodialysis (SED). Consequently, the resulting MOF membrane achieves a Li + flux of 1.17 mol·m −2 ·h −1 and exhibits a Li + /Mg 2+ permselectivity 14.3 times higher than that of the unmodified membrane, alongside excellent long-term operational stability. This environmentally friendly lithium extraction strategy advances the development of high-performance separation membranes and holds great promise for key applications such as lithium recovery from salt-lake brines, offering an innovative technological pathway toward efficient strategic resource recovery and the advancement of a circular economy. The synergistic dual-confined mechanism governs the selective Li + /Mg 2+ sieving performance of the MOF membrane. Download: Download high-res image (146KB) Download: Download full-size image
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2025
·
IF 9
Haofan Wang,Zhifei Wu,Xu Zhang,Li Liu,Deqing Liu,Jin Ran,Dawei Zhang
Conventional polymer anion exchange membranes (AEMs) suffer from the permeability-selectivity trade-off in diffusion dialysis (DD), limiting their efficiency in critical resource recovery scenarios (e.g., acid recycling and Li + extraction). To overcome this, this study incorporated polyaniline-modified MXene (PANI-Ti 3 C 2 T X ) nanosheets as transformative fillers into quaternized polyphenylene oxide (QPPO). The resulting PANI-Ti 3 C 2 T X -QPPO membranes enable dual-function DD for H + /metal cations and Li + /Mg 2+ separation. First, the as-prepared membranes exhibited enhanced microphase separation, yielding expanded hydrophilic domains (13.95–14.8 nm vs. 12.5 nm in pristine QPPO). Moreover, the 1.0 %-PANI-Ti 3 C 2 T X -QPPO membrane (with 1.0 wt% filler loading) achieved a peak ion exchange capacity of 1.75 mmol g −1 . For H + /metal cations separation: in HCl/FeCl 2 mixture, the H + dialysis coefficient ( U H ) reached 1.39–1.50 × 10 −2 m h −1 (2.7–2.9 times higher than the commercial TWDDA3S, 0.52 × 10 −2 m h −1 ); in HCl/AlCl 3 mixture, U H reached 1.50–1.53 × 10 −2 m h −1 , combined with exceptional selectivity ( S H/Al = 1568.4–1805.8), outperforming both TWDDA3S ( U H = 0.94 × 10 −2 m h −1 , S H/Al = 1423.8) and pristine QPPO ( U H = 1.27 × 10 −2 m h −1 , S H/Al = 1117). Finally, for Li + /Mg 2+ separation, the membranes delivered enhanced Li + flux with competitive S Li/Mg (11.4–12.4) against TWDDA3S (11.4) and QPPO (11.8). This study demonstrates that PANI-Ti 3 C 2 T X and QPPO synergistically overcome the permeability-selectivity trade-off in polymer membranes.
研究领域:
膜科学与技术
·
分离工程
·
材料化学
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资源回收
·
离子传输
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DOI
高影响因子
危险品化学品经营许可证（带存储）